Background of the invention
[0001] This invention relates to a novel polyester composition having ultraviolet light
penetration reduction characteristics use to manufacture polyester bottles. Specifically,
this invention relates to a polyester composition comprising azimido-benzene (benzotriazole)
ultraviolet absorbent, 2, 6 naphthalene dicarboxylate comonomer and pre-polymerized
polyester. In addition to having ultraviolet penetration blocking characteristics,
the polyester composition of this invention is capable of producing polyester bottles
with haze values maintained at commercial acceptable levels.
Prior arts
[0002] Polyester resins use to manufacture polyester bottles include, but are not limited
to, polyethylene terephthalate ( "PET"), modified polyethylene terephthalate, polybutylene
terephthalate ("PBT") and polytrimethylene terephthalate (PPT). PET is the most commonly
used polyester. PET is used to manufacture packaging materials, polyester bottles
for containing drinks/beverages, such as aerated water, fruit juice, tea and forms
of other edible materials. PET is the polymer of choice because of its lightness as
compared to other polymers, its remarkable elasticity, good storability and its light
penetration prevention characteristics
Problems to be solved
[0003] Generally most polyester containers, irrespective of its polymer constituents, when
exposed to sunlight over a period of time will deteriorate and fade after absorbing
ultraviolet light. Most food ingredients are photo-chemically influenced by ultraviolet
light with wavelengths between 200∼ 380 nm To protect food ingredients from being
altered photo-chemically, polymers used in the manufacture of packaging and bottles
must absorb ultraviolet light with wavelengths between 200nm∼380nm. Most contemporaneous
polyester packaging, containers and bottles, etc. do not absorb ultraviolet light
between 200 nm -380nm. For example, PET, the most common polyester bottle ingredient,
absorbs ultraviolet light below wavelengths less than 315 nm. Thus how to manufacture
polyester bottles with ingredients capable of absorbing ultraviolet light with wavelengths
between 315 ∼ 380nm is essential. To manufacture polyester bottles with ultraviolet
absorbing characteristics, the traditional approach is to add ultraviolet absorbents
into polyester compositions used to manufacture the bottles.
[0004] Ultraviolet absorbents can be divided into organic ultraviolet absorbents and inorganic
ultraviolet absorbents. Examples of organic ultraviolet absorbents are salicylate,
benzophenone, and azimido.benzene (benzotriazole). Organic absorbents utilize their
individual resonance structures to absorb ultraviolet light of various wavelengths.
Examples of inorganic absorbents are titanium dioxide, zinc oxide, ferric oxide and
cerium oxide. In contrast to their organic counterparts, inorganic absorbents disperse
and absorb ultraviolet rays by possessing the requisite particle sizes, having particles
with high refractive index and particles with the requisite tinct characteristics.
[0005] Attempts have been made to manufacture polyester containers with ultraviolet hiding
effect spanning wavelengths between 315 nm ∼ 380 nm. Japanese Patent Application Laid
- Open No. 10-53696 discloses manufacturing polyester bottles with co-polyester containing
naphthalene co-monomer, an organic absorbent, of 0.001 - 10 % weight. But absorption
of ultraviolet light in naphthalene co-monomer was determined to be below 360nm wavelengths
only, and thus will be unsuitable for protecting a wide range of beverages/drinks
from deterioration caused by exposure to ultraviolet light. This is because the resonance
structure of naphthalene with two benzene rings does not wholly absorb and reduce
the penetration effect of ultraviolet rays.
[0006] Other attempts to manufacture polyester bottles with ultraviolet hiding effect above
360nm wavelengths teach the use of inorganic absorbents rather than organic absorbents.
The usual approach is to add small amount of inorganic absorbents such as titanium
dioxide, zinc oxide, ferric oxide and cerium oxide, etc. to a polyester composition.
These inorganic absorbents are particles with sizes ranging from 0.01 to 2.0 µm. Although
using inorganic particles of such small size will initially have favorable dispersion
and absorption effect on ultraviolet light of wavelength over 360nm, overtime the
inorganic particles will coagulate and reduce their original penetration hiding effect
against ultraviolet light.
[0007] If particles between 0.01∼2.0 micrometers are used to manufacture thick polyester
bottles, such as 0.355 millimeter thick polyester bottles, the addition level of the
inorganic particles would have to exceed 1000ppm to compensate for the small inorganic
absorbent particle sizes. The large use of inorganic particles in excess of 1000 ppm
would increase the haze values of the polyester bottles manufactured.
[0008] It is an object of this invention to further improve the ultraviolet hiding effect
of polyester bottles, while maintaining or lowering the haze value of the manufactured
bottles.
[0009] Another object of this invention is to manufacture polyester bottles with a polyester
composition comprising naphthalene, azimido-benzene and pre-polymerized polyester.
[0010] Still another object of this invention is to use critical mole and concentration
ratios of naphthalene, azimodo-benzene and pre-polymerized polyester to form the polyester
composition of this invention use to manufacture polyester bottles with reduced ultraviolet
light penetration characteristics and with commercially acceptable haze value levels.
Summary of the invention
[0011] This invention relates to a polyester composition use to manufacture polyester bottles
with ultraviolet light penetration blocking characteristics. The polyester composition
comprises naphthalene, azimodo-benzene and pre-polymerized polyester. In addition
tohaving ultraviolet penetration blocking characteristics, the polyester composition
of this invention is capable of producing polyester bottles with haze values maintained
at commercial acceptable levels.
[0012] The polyester composition of this invention results from mixing preferably 10-1000
ppm of azimido-benzene ultraviolet absorbent with preferably 0.01 to 2 mol% of2, 6-naphthalene
dicarboxylate comonomer and pre-polymerized polyester of preferably over 98 mol%.
[0013] Specifically, this invention uses Ciba Geigy Corporation's TINUVIN * 234 as the preferred
organic absorbent of choice. Like other organic absorbents, TINUVIN * 234 absorbs
ultraviolet rays by the use of its special resonance structure. The hydroxy (OH) group
and the nitrogen (N) group of the TINUVIN * 234 absorbent form inner molecular hydrogen
bonding, which causes resonance effect and absorb ultraviolet rays.
[0014] The process through which 2,6-naphthalene dicarboxylate and TINUVIN * 234 ultraviolet
absorbent are added to the polyester composition begins with milling 2,6-naphthalene
dicarboxylate into powder form and adding ethylene glycol (EG) to form a slurry.
Detailed description of the invention
[0015] To produce polyester bottles capable of absorbing and reducing ultraviolet light
penetration at variable wavelengths, the inventor repeated careful review and research,
proposes to manufacture polyester bottles with polyester composition comprising naphthalene
co-monomers and azimido-benzene ultraviolet absorbent. Polyester bottles manufactured
with a polyester composition comprising naphthalene and azimido-benzene produced two
significant results: bottles were found to drastically reduce ultraviolet light penetration;
and their haze values were kept at a commercial acceptable levels.
[0016] A wide range of polyester resins can be used as starting materials for this invention.
Generally polyester resins are produced from esterifying of a dibasic acid and a diol,
or by transesterifying a diester such as dimethyl terephthalate (DMT) and a diol.
The most used dibasic acid is terephthalic acid (TPA), modified or unmodified, and
the most used diol is ethylene glycol (EG). It is well known that polyester resin
compositions can consist of two or more dibasic acid and/or two or more diols. Example
of dibasic acid ingredients that may be used to manufacture the polyester resin of
this invention are iso-phthalic acid, succinic acid, glutaric acid, adipic acid, sebacic
acid and/or mixtures of analog comprising any of the previously mentioned dibasic
acids. Example of diol ingredients that may be used to manufacture the polyester resin
of this invention are diethylene glycol, 1,3 - propane glycol, 1,4-butane glycol and/or
mixture of analog of any of the previously mentioned diol.
[0017] A common method of manufacturing polyester resins for manufacturing polyester bottles
, which is reacting terephthalic acid and ethylene glycol preferably between 210 to
240°C to form monomer and water. Water is continuously removed during reaction of
the terephthalic acid with the ethylene glycol. During the reaction, a catalyst is
not required because adding a catalyst will slightly speed up the reaction and reaction
enhancement are not noticeable. However, addition of catalyst increases the undesired
side product diethylene glycol (DEG). After finishing esterification of terephthalic
acid and ethylene glycol, the reaction is subsequently subject to condensation reaction
comprising a pre-polymerization reaction and a main polymerization reaction.
[0018] The pre-polymerization reaction occurs preferably between 270∼280°C and at an operating
vacuum pressure preferably between 250∼15 mmHg. The main polymerization occurs preferably
between 275 to 285°C and at an operating vacuum pressure preferably below 1 mmHg.
At these preferred temperatures and pressures the polycondensation reaction is successfully
performed. At the end of polycondensation of the PET melt phase, intrinsic viscosity
(IV) value of PET polymer usually increases from about 0.5 to 0.7 dl/g. At this point,
the polymer is uploaded to the cooling water bath for quick chilling and subsequently
cut into cylindrical polyester chips.
[0019] In order to increase the intrinsic viscosity (IV) value of the PET polymer to obtain
the desired polymer required to manufacture the polyester bottles, solid phase polymerization
of the polyester chips is performed at 200°C in the presence of nitrogen gas atmosphere,
which increases the IV value to between 0.7 to 1.1 dl/g, preferably between 0.72∼0.88
dl/g. If the temperature of the solid phase polymerization is lower than 200°C, the
intrinsic viscosity (IV) value slowly increases or even not to proceed the solid phase
polymerization. At temperature below 200°C, the chances of performing a successful
solid phase polymerization reaction needed to produce the desired polymer films are
greatly reduced. The next series of steps involve crystallizing and drying the polyester
chips, molding the ester particles into parisons through the use of bottle blowing
machine, and then blowing the polyester chips to obtain bottles of desired shapes.
[0020] Manufacturing polyester bottles from resin compositions -lacking ultraviolet protection
- using traditional methods as discussed above render bottles' contents vulnerable
to ultraviolet irradiation. To overcome the effect of ultraviolet radiation on polyester
bottles' contents, this invention teaches mixing preferably 10-1000ppm of azimido-benzene
ultraviolet absorbent with preferably 0.01 to 2 mol% of 2.6 - naphthalene dicarboxylate
comonomer and with pre-polymerized polyester of preferably over 98 mol%. Using the
precise composition ranges specified in this paragraph for manufacturing is critical
for reducing ultraviolet light penetration through the manufactured polyester bottles,
while keeping the manufactured polyester bottles haze value levels to a minimum.
[0021] The ultraviolet wave crest absorption wavelengths of naphthalene are located at 286nm
and 312 nm, the hydrogen atom at its 2,6 position of naphthalene is replaced with
COOCH
3 to form 2, 6- naphthalene dicarboxylate. When polyester composition containing 2,
6- naphthalene dicarboxylate is exposed to ultraviolet light, the ultraviolet wave
crest absorption wavelengths of 2, 6- naphthalene dicarboxylate shift to 345nm and
365 nm. Thus, addition of small amount of naphthalene dicarboxylate in polyester synthesis
results in a polyester composition capable of effectively absorbing ultraviolet light
below wavelength 360 nm. Naphthalene dicarboxylate is easily linked into the molecular
chain of the polyester resin during the polymerization process. The polyester composition
containing naphthalene co-monomer is fused and blown molded to extend parallel along
the bottles heading due to the molecular chain is the plane of dual benzene ring structure
of the naphthalene, thereby maximizing the absorption hiding efficiency against ultraviolet
irradiation.
[0022] To achieve even higher ultraviolet absorption efficiency, absorption above 360 nm
wavelengths, this invention teaches the addition of organic ultraviolet absorbent,
such as salicylate, benzophenone, and azimido-benzene (benzotriazole) etc into the
polyester composition. These organic absorbents effectively absorb ultraviolet irradiation
by the use of their special resonance structures. Through extensive research, the
organic absorbent azimido-benzene has proven to be very effective against ultraviolet
irradiation. Specifically, this invention uses Ciba Geigy Corporation's TINUVIN *
234 as the preferred organic absorbent of choice. Like other organic absorbents, TINUVIN
* 234 absorbs ultraviolet irradiation by the use of its special resonance structure.
The hydroxy (OH) group and the nitrogen (N) group of the TINUVIN * 234 absorbent form
inner molecular hydrogen bonding, which causes resonance effect and absorb ultraviolet
irradiation. The electric resonance plane of azimido-benzene is larger than that of
other organic absorbents, such as salicylate and benzophenone, results in ultraviolet
absorption along a wider wavelength spectrum. This invention has shown that mixing
a small amount of TINUVIN * 234, between 10 and 1000ppm, with polyester to form a
polyester resin composition was effective against ultraviolet irradiation below wavelengths
of 360nm. The polyester resin composition containing TIIVWIN * 234 was not as effective
against ultraviolet irradiation below wavelengths of 360 nm, as compared with polyester
resin composition containing 0.01∼2 mol% naphthalene co-monomer. However, the reverse
was determined to be true when tested against ultraviolet irradiation above wavelengths
of 365nm.
[0023] The inventor has discovered that by mixing both naphthalene co-monomer and organic
ultraviolet absorbent TINUVIN * 234 with polyester resin to form a polyester composition,
it was indeed possible to drastically reduce ultraviolet penetration below 360nm and
above 360nm without increasing the haze value of the polyester composition.
[0024] The addition level of the 2,6 - naphthalene dicarboxylate to the polyester composition
should be between 0.01 and 2.0 mol %, preferably between 0.1 nd 1.0 mol %. When the
addition level of 2,6 - naphthalene dicarboxylate falls below 0.1% mol, the ultraviolet
hiding effect for wavelengths below 360nm is not apparent. When the addition level
of 2,6 - naphthalene dicarboxylate is above 1.0% mol, the ultraviolet hiding effect
for wavelength below 360nm is moderate at best.
[0025] The addition level of the TINUVIN * 234 to the polyester composition should be between
10-1000 ppm, preferably between 200 - 500 ppm. When the addition level of TINUVIN
*234 is below 200 ppm, the ultraviolet hiding effect for wavelengths above 370 nm
is not apparent. When the addition level of TINUVIN * 234 is above 500 ppm, the ultraviolet
hiding effect for wavelengths below 370nm is moderate at best.
[0026] The process through which 2,6-naphthalene dicarboxylate is added to the polyester
composition begins with the milling of 2,6-naphthalene dicarboxylate into powder form
and adding ethylene glycol (EG) to form a 25 wt % slurry, which is then poured into
a reaction vessel by means of gear pumps. The slurry containing 2,6-naphthalene dicarboxylate
can be added into the polyester process during the slurry preparation of the diacid
and glycol or during the esterification reaction process. Similarly, the TINUVIN *
234 absorbent is added to ethylene glycol (EG) to form 15 wt % slurry, and then poured
into a reaction vessel via gear pump. The slurry containing TINUVIN * 234 absorbent
can be added into the polyester process during the slurry preparation of the diacid
and glycol or during the esterification reaction process..
[0027] Different additive such as thermal stabilizer, light stabilizer, dye, colorant, plasticizer,
antioxidant, infra red absorbents and anti-ultraviolet agents, and UV-resistant agent,
etc. can be added into the polyester composition of this invention.
[0028] The instrument used to measure the ultraviolet penetration analysis of the polyester
bottle pieces is the ultraviolet spectrometer model SHIMADZU UV 2101PC. Scan and measure
the ultraviolet penetration rate of wavelength 300∼400nm.
[0029] The instrument used to measure the haze value level is the color and color difference
meter, model 1001 DP manufactured by NIPPON DENSHOKU KOGYO CO. LTD.
[0030] By way of examples, the manufacturing processes, conditions and process components,
though not limited to the examples, of the present invention may be as follows:
Examples
(Example 1)
[0031] PET oligomer 12.11 Kg and EG 3.87 Kg are added into an electric heated stainless
steel 30 litre reactor, agitated and heated under atmosphere to 260°C, and EG in the
amount of 1200-1400 ml is collected. Before the polycondensation reaction, the following
ingredients are subsequently added: condensation catalyst of 450 ppm antimony acetate,
140 ppm cobalt acetate, 0.25mol % 2,6- naphthalene dicarboxylate and 300ppm TINUVIN*234
organic ultraviolet absorbent.
[0032] Next, the reactor is vacuumed to pressures below 1 mmHg to perform the pre-polymerization
reaction at a temperature of 270°C, and to subsequently perform the main polymerization
reaction at 280°C to produce the co-polyester resins. During this process, the intrinsic
viscosity of the co-polyester is controlled between 0.6 - 0. 64dl/g. The resulting
polymer is cut into chips, dried and crystallized for 6 hours under 180°C nitrogen
atmosphere. The resulting mixture undergoes solid phase polycondensation reaction
at reaction temperature of 225°C for 20 hours and with an intrinsic viscosity between
0.76 - 0.86 dl/g. After the solid phase polycondensation process, the polyester chips
are processed into polyester bottles by 280°C injection molding machine.
[Example 2-3]
[0033] These examples are similar to Example 1, except that adjustments are made to the
addition level of 2,6-naphthalene dicarboxylate and TINUVIN*234. See table 1 for results
below.
(Comparative Example 1)
[0034] PET oligomer 12.11 Kg and EG 3.87 Kg are added into an electric heated stainless
steel 30 litre reactor, agitated and heated under atmosphere to 260°C; and EG in the
amount of 1200-1400ml is collected. Before the polycondensation reaction, the following
ingredients are subsequently added: polycondensation catalyst of 450 ppm antimony
acetate, 140 ppm cobalt acetate.
[0035] Next, the reactor is vacuumed to pressures below 1 mmHg to perform the pre-polymerization
reaction at a temperature of 270°C, and to perform subsequently the main polymerization
reaction at 280°C to produce the co-polyester resins. During this process, the intrinsic
viscosity of the co-polyester is controlled between 0.6 - 0.64dl/g. The resulting
polymer is cut into granules, dried and crystallized for 6 hours under 180°C nitrogen
atmosphere. The resulting mixture undergoes solid phase polycondensation reaction
at reaction temperature of 225°C for 20 hours and with an intrinsic viscosity between
0.76 - 0.86 dl/g. After the solid polycondensation process, the polyester chips are
processed into polyester bottles by 280°C injection molding machine
(Comparative Example 2)
[0036] PET oligomer 12.11 Kg and EG 3.87 Kg are added into an electric heated stainless
steel 30 litre reactor, agitated and heated under atmosphere to 260°C, and EG in the
amount of 1200-1400ml is collected. Before the olycondensation reaction, the following
ingredients are subsequently added: polycondensation catalyst of 450 ppm antimony
acetate, 140 ppm cobalt acetate, and 0.25mol % 2,6- naphthalene dicarboxylate. Next,
the reactor is vacuumed to pressures below 1 mmHg to perform the pre-polymerization
reaction at a temperature of 270°C, and to subsequently perform the main polymerization
reaction at 280°C to produce the co-polyester resins. During this process, the intrinsic
viscosity of the co-polyester is controlled between 0.6 - 0.64dl/g. The resulting
polymer is cut into chips, dried and crystallized for 6 hours under 180°C nitrogen
atmosphere. The resulting mixture undergoes solid phase polycondensation reaction
at reaction temperature of 225°C for 20 hours and with an intrinsic viscosity between
0.76 - 0.86 dl/g. After the solid phase polycondensation process, the polyester chips
are processed into polyester bottles by 280°C injection molding machine.
(Comparative Examples 3-6)
[0037] The operation is similar to example 2, except that the addition levels of 2,6-naphthalene
dicarboxylate and TINUVIN*234 are adjusted. See table 1 results below.
[0038] From table 1 below, it is observed that addition of 0.25 mol % 2,6- naphthalene dicarboxylate
alone to the polyester composition had little effect on ultraviolet radiation over
360nm wavelengths. Similarly, addition of TINUVIN*234 alone had poor hiding effect
against ultraviolet radiation above and at 360 nm wavelengths. In contrast, the polyester
bottle slightly mixed with 2,6 - naphthalene dicarboxylate and TINUVIN *234 drastically
reduced ultraviolet penetration; while maintaining haze value levels at a minimum.
(Comparative Example 7)
[0039] Except for adding 0.25mol% of 2,6-naphthalene dicarboxylate and 50 ppm of 20nm ferric
oxide inorganic ultraviolet absorbent to instead of adding TINUVIN*234, comparative
example 7 is similar to example 1. See table 2 for results below.
(Comparative Example 8)
[0040] Comparative example 8 is similar to Comparative example 7, except that the addition
level of the 20nm ferric oxide inorganic ultraviolet absorbent is 100ppm instead of
50 ppm. See table 2 for results below.
(Comparative Example 9)
[0041] Comparative example 9 is similar to Comparative example 7, except that the particle
size and addition level of the ferric oxide inorganic ultraviolet absorbent are 0.27
µm and 200 ppm respectively. See table 2 for results below.
[0042] From table 2, the smaller the size of inorganic absorbent particles added to the
polyester composition mixed with 0.25% mol of 2,6-naphthalene dicarboxylate, the higher
the absorbent addition level added. Increased addition level of the inorganic absorbent
results in secondary coagulation, reduces penetration effect against ultraviolet radiation
and results in higher haze values.
Table 1
| |
2,6-Naphthalene dicarboxylate (NDC) mol% |
Addition level of TINUVIN * 234 ppm |
Haze |
Ultraviolet penetration rate |
Ultraviolet penetration rate |
Ultraviolet penetration rate |
| |
|
|
|
T% at 360nm |
T% at 370nm |
T% at 380nm |
| Example 1 |
0.25 |
300 |
0.7 |
6.5 |
47.5 |
66.5 |
| Example 2 |
0.25 |
500 |
0.4 |
9.7 |
47.4 |
64.3 |
| Example 3 |
0.50 |
500 |
0.4 |
2.4 |
38.0 |
61.6 |
| Comparative example 1 |
0 |
0 |
1.1 |
70.8 |
78.4 |
81.6 |
| Comparative example 2 |
0.25 |
0 |
1.1 |
15.0 |
69.2 |
80.5 |
| Comparative example 3 |
0 |
300 |
1.6 |
50.2 |
60.5 |
68.6 |
| Comparative example 4 |
0 |
600 |
0.4 |
37.3 |
47.3 |
59.0 |
| Comparative example 5 |
0.25 |
100 |
0.4 |
15.6 |
63.8 |
75.7 |
| Comparative example 6 |
0.10 |
500 |
0.4 |
25.4 |
56.2 |
67.6 |
Table 2
| |
2,6-Naphthalene dicarboxylate (NDC) mol% |
Ferroferric oxide |
Haze |
Ultraviolet penetration rate |
Ultraviolet penetration rate |
Ultraviolet penetration rate |
| |
|
Addition level ppm |
Particle size |
|
T% at 360nm |
T% at 370nm |
T% at 380nm |
| Comparative example 7 |
0.25 |
50 |
20 nm |
1.1 |
14.1 |
63.1 |
74.8 |
| Comparative example 8 |
0.25 |
100 |
20 nm |
1.5 |
14.1 |
61.2 |
71.8 |
| Comparative example 9 |
0.25 |
200 |
0.27µm |
9.4 |
13.0 |
58.3 |
69.8 |
The present invention comprises the following preferred embodiments:
[0043]
1. An UV-resistant polyester composition capable of being blown molded into polyester
bottles/vessels of desired shapes comprising:
(a) azimido-benzene ultraviolet absorbent; and
(b) copolyester
2. The UV-resistant polyester composition according to embodiment 1, wherein said
ultraviolet absorbent concentration added to said copolyester is between 10-1000ppm.
3. The UV-resistant polyester composition according to embodiment 2, wherein said
copolyester comprises 2,6 - naphthalene dicarboxylate and prepolymerized polyester.
4. The UV-resistant polyester composition according to embodiment 3, wherein said
prepolymerized polyester comprises polyethylene terephthalate and modified polyethylene
terephthalate.
5 The UV-resistant polyester composition according to embodiment 4, wherein said 2,
6-naphthalene dicarboxylate is between 0.01 to 2 mol% of the copolyester.
6. The UV-resistant polyester composition according to embodiment 4, wherein said
prepolymerized polyester constitutes over 98% mol of the copolyester.
7. The UV-resistant polyester composition according to embodiment 4 wherein said 2,6-naphthalene
dicarboxylate addition level to form the copolyester is between 0.01 to 2 mol% and
said prepolymerized polyester addition level to form the copolyester is over 98 mol%
respectively.
8. The UV-resistant polyester composition according to embodiment 7, wherein said
2,6-naphthalene addition level is between 0.1-1.0 mol%.
9. The UV-resistant polyester composition according to embodiment 4, wherein said
2,6-naphthalene dicarboxylate in-process mixture comprises 25 wt % milled 2,6-naphthalene
dicarboxylate and ethylene glycol slurry.
10. The UV-resistant polyester composition according to embodiment 5, wherein said
2,6-naphthalene dicarboxylate in-process mixture comprises 25 wt% milled 2,6-naphthalene
dicarboxylate and ethylene glycol slurry.
11. The UV-resistant polyester composition according to embodiment 6, wherein said
2,6 naphthalene dicarboxylate in-process mixture comprises 25 wt % milled 2,6-naphthalene
dicarboxylate and ethylene glycol slurry.
12. The UV-resistant polyester composition according to embodiment 7, wherein said
2,6-naphthalene dicarboxylate in-process mixture comprises 25wt% milled 2,6-naphthalene
dicarboxylate and ethylene glycol slurry.
13. The UV-resistent polyester composition according to embodiment 8, wherein said
dicarboxylate in-process mixture comprises 25wt% milled 2,6- naphthalene dicarboxylate
and ethylene glycol slurry.
14. The UV∼resistant polyester composition according to embodiment 1, wherein said
ultraviolet absorbent is Ciba Geigy's TINUVIN * 234.
15. The UV-resistant polyester composition according to embodiment 12, wherein said
ultraviolet absorbent is Ciba Geigy's TINUVIN * 234.
16. The UV-resistant polyester composition according to embodiment 14, wherein the
addition level of TINUVIN* 234 is between 200 to 500 ppm.
17. The UV-resistant polyester composition according to embodiment 15, wherein the
addition level of TINUVIN * 234 is between 200 to 500 ppm.
18. The UV-reisistant polyester composition according to embodiment 17, wherein said
composition further comprises antioxidant, organic pigment and infrared absorbent.
19. The UV-resistant polyester composition according to embodiment 18, wherein the
2,6-naphthalene dicarboxylate slurry is added to the copolyester during mixing of
naphthalene diacid and glycol or the during the esterification reaction.
20. The UV-resistant polyester composition according to embodiment 16, wherein said
composition further comprises antioxidant, organic pigment and infrared absorbent.
1. An UV-resistant polyester composition capable of being blown molded intopolyester
bottles/vessels of desired shapes comprising:
(a) azimido-benzene ultraviolet absorbent; and
(b) copolyester
2. The UV-resistant polyester composition according to claim 1, wherein said ultraviolet
absorbent concentration added to said copolyester is between 10- 1000ppm, and/or wherein
said copolyester comprises 2,6 - naphthalene dicarboxylate and prepolymerized polyester.
3. The UV-resistant polyester composition according to claim 2, wherein said pre-polymerized
polyester comprises polyethylene terephthalate and modifiedpolyethylene terephthalate
4. The UV-resistant polyester composition according to one or more of the preceding claims,
wherein said 2, 6-naphthalene dicarboxylate is between 0.01 to 2 mol% of the copolyester,
and/or wherein said prepolymerized polyester constitutes over 98% mol of the copolyester.
5. The UV-resistant polyester composition according to one or more of the preceding claims,
wherein said 2,6-naphthalene dicarboxylate addition level to form the copolyester
is between 0.01 to 2 mol% and said prepolymerized polyester addition level to form
the copolyester is over 98 mol% respectively, and/or wherein said 2,6-naphthalene
addition level is between 0.1-1.0 mol%.
6. The UV-resistant polyester composition according to one or more of the preceding claims,
wherein said 2,6-naphthalene dicarboxylate in-process mixture comprises 25 wt % milled
2,6-naphthalene dicarboxylate and ethylene glycol slurry
7. The UV∼resistant polyester composition according to one or more of the preceding claims,
wherein said ultraviolet absorbent is Ciba Geigy's TINUViN * 234.
8. The UV-resistant polyester composition according to claim 7, wherein the addition
level of TINUVIN* 234 is between 200 to 500 ppm.
9. The UV-reisistant polyester composition according to one or more of the preceding
claims, wherein said composition further comprises antioxidant, organic pigment and
infrared absorbent.
10. The UV-resistant polyester composition according to one or more of the preceding claims,
wherein the 2,6- naphthalene dicarboxylate slurry is added to the copolyester during
mixing of naphthalene diacid and glycol or the during the esterification reaction.